New chromiferous monoazo-dyestuffs



United States Patent I NEW CHROMIFEROUS MONOAZO-DYESTUFFS Arthur Buehler, Rheinfelden, Alfred Fasciati, Bottmingen, and Henri Riat, Arlesheim, Switzerland, assignors to Ciba Limited, Basel, Switzerland, a Swiss firm No Drawing. Filed Aug. 11, 1958, Ser. No. 754,165

Claims priority, application Switzerland Aug. 14, 1957 9 Claims. (Cl. 260-145) This invention provides new chromiferous monoazodyestufis which contain one atom of chromium bound in complex union to two molecules of difierent monazodyestuffs, of which dyestutts only one contains a halogen- 1:3:5-triazine grouping containing at least one halogen atom and at least one of which contains an acid' group imparting solubility in water, more especially a sulfonic acid group. The invention provides more especially 1:2- complex chromium compounds which contain two molecules of ditterent dyestuifs as specified above and contain only one dichloroor monochloro-1:3:5-triazine radical, which may be bound through a nitrogen bridge and is advantageously of the formula imparting'solubility in water such as a carb'oxylic acid or sulfonicacid group. Such groups may be present in any "suitable positions, for example, in the radical of the coupling component or diam-component or in the monohalogen-triazine radical, "for example, in the group R of the radical of the Formula 1. v

"In-addition to such groups, which may be present in both or only one of the monoazo-dyestutts present in the complex chromium compound, there must be present in one, of these monoazo-dyestufis a 2:4-dichloro-1:3 :5-triazine radical or a monohalogenated triazine radical, for

example, a 2-chloro 4-alkyl-, 4-aryl-, 2-chloro-4-alkoxy or -4-aryloxy- 1:3:5-triazine radical or a radical of the Formula 1, which radical is bound to the radical of the diazo component or coupling component advantageously through an amino group of the formula in which n is a whole number, for example, 2 or'l.

The asymmetrical complex chromium compounds of metrical l-:-2-chromium complex, and using monoazo-dyeice Patented J nine 28, 1960 2 stuffs of which one, advantageously the metal-free-dyestufi contains a triazine nucleus of the kind defined above. Alternatively the said triazine radical may be'incorporated into the appropriate asymmetrical chromiferous dyestufi not containing ahalogen-triazine radical. For this purpose one of the three chlorine atoms ina trihalogentria zine, especially cyanuric chloride (2:4:6-trichloro- 1:3:5-triazine), may be replaced by the radical of a 1:2- complex chromium compound which contains a monoazodyestuit containing an acylatable mercapto or hydroxyl group or advantageously an acylatable amino group, or one ofthe aforesaid chromiferous dyestuffs containing an acylatable group may be condensed with a 2:4-dichloro- 1:3:5-triazine which contains in the 6-position a free amino group or an organic substituent, for example, a dihalogen-triazine of the formula ilalogen in which R represents an advantageously organic radical, for example, the condensation taking place, for example, at the acylatable group and resulting in the replacement of only one of the two halogen atoms. 7

Thedihalogen-triazines of the Formula 2 can ,be made ,by methods in themselves known from cyanuric halides such as cyanuric bromide, orcyanuricchloride, by reacting, for example, one molecular proportion of cyanuric chloride with one molecular proportion of a reactive 7 organic mercap'to or hydroxy-compouncl (for example, a phenol or 'alcohol), or with one molecular proportion of ammonia or with one molecular proportion of an organic at most secondary and advantageously primary amine not having the character of a dyestult and which contains'at least one group imparting solubility in water, if it is to be combined with a dyestutf free frorn groups imparting mentioned, for example, aliphatic or aromatic mercaptoor hydroxy-compounds, especially lower alcohols such as methyl alcohol, or phenols, 'thiophenols, and also methylamine, ethylamine, isopropylamine, methoxyethyla mine, methoxypropylamine, cyclohexylamine, dimethylamine, diethylamine, 'N-methylphenylamine, chlorethylamine, ethanolamines, piperidine, morpholine, ,aminoc'arbonic acid esters, aminoacetic acid ethyl ester, hydrazine,

phenyl-hydrazine, aniline .or ammonia or, if desired,

amines containing groups imparting solubility .in wate r such as aminoethane sulfonic acid, N-methylamino ethane sulfonic'acid, ortho-, metaor para-aminobenzoic acids or sulfo-aminobenzoic acids, ortho-, metaorparaaminobenzene sulfonic acids, aminonaphthalene sulfonic acids, for example, 2-aminonaphthalene-4:8-disulfonic acid.

condensation with the primary cyanuric chloride condensation products of the Formula 2so obtained,- can be made plexes to be formed.

Mixed complex chromium compounds, which contain anlacylatable amino group, can also be-made by the subj As such compounds there maybe The metalliferous dyestuffs, which are to be used for 3 sequent reduction of a nitro group or hydrolysis of an acylamino group present in a complex chromium compound.

As starting materials for use in the process two difierent monoazo-dyestuifs are required, of which one may be'an ortho: ortho'-dihydroxy-mo noazo-dyestufi, an-ortho- ;carboxy ortho'-hydroxy-monoazo-dyestufi or an orthohydroxy-ortho' amino-monoazo-dyestutf and the other is advantageously an or'tho:ortho dihydroxy monoamino- 'azo dyestufi. There are advantageously used ortho: ortho'-dil1ydroxy-monoazodyestuffs or chromium compounds (Isl-complexes) thereo'fwhich contain-one-atom 'of chromium bound in complex union perdyestuff molecule. Alternatively, there may be used ortho-carboxyortho hydroxymonoazo-dyestuffs or ortho-hydroxy- 'ortho-amino-monoazo-dyestuffs :or their lzl-complexes. T he necessarymonoazo-dyestufis which are usedrin-the process free from metal or inrthe form of 1': l-metal complexes can be made by methods in themselves known by coupling ortho-carboxyor ortho-hydroxy-diazo-compounds, especially those of the benzene or naphthalene series, with coupling components capable of coupling in a. position vicinal to a hydroxyl group or to an enolizable keto group or to an amino group. As will be understood from the foregoing description, the components advantageously contain groups imparting solubility in water. Furthermore, the components are so selected that only one of the two starting materials to be used, namely the chromiferous or chromium-free monoazo-dyestufi, contains a single acylatable group, more especially an at mostsecondaryamino group, or a substituent subsequently convertible into such group.

Taking into account the foregoing requirements the following components, for example, maybe used for making the monoazo-dyestuffs:

As diazo-compounds there are advantageously used those of ortho-carboxy-amines of the benzene series and above all those of ortho-hydroxy-amines of the benzene or naphthalene series, which contain, in addition to the carboxyl or ,hydroxyl group and the amino group, further substituentssuch as nitro groups, halogen atoms, for example, chlorine; alkyl groups, for example, methyl groups; alltoxy groups, for example, .methoxy groups; or ,acylamino'groups, especially those containing a few, for example, at most four, carbon atoms, ,for example, acetylamino groups; and also sulfonic acid groups. As .examples .of suitable diazo compounds there may -b mentioned:

Z-aminobenzoic acid,

"-chloro-2-a1ninobenzoic acid,

'2-amino-l-hydroxybenzene,

"4-or 5 chloro-Z-aminol hydroxybenzene, "4-, 5- or-6-nitro-2-amino-l hydroxybenzen'e,

As coupling components there may be used tho e QaP and 4 ble of coupling in a position vicinal to a primary or secondary amino group or a hydroxyl group, "especially aminonaphthalenes and naphthols. There are also suitable keto-compounds which are capable of coupling in a position vicinal to the enolized or enolizable keto group, especially l-phenyl-3-methyl-5-pyrazolones.

As examples of coupling components there may be mentioned:

(a) Coupling components which contain no acylatable group after coupling: Hydroxybenzenes, .such as para-,cresol tor para-tertiaryamylphenol, 4-methyl-2-acetylamino-l hydroxybenzene, 4-acetylamino-l-hydroxybenzene, fi-Ketocarboxylic acid esters or -am'ides,'such as Acetoacetic acid anilideand 1-acetoacetylamino-2-, -3- or -4-chlorobenzene, 5-pyrazolones, such as '3-methyl-5-pyrazolone, 1phenyl-3-methyl 5-pyrazolone, l 3 -diphenyl-S-pyrazolone, '1-(2-, 3'- or 4'-chlorophenyl) -3-methyl-'5-pyrazolone, 1-(2 :5 '-dichlorophenyl -3 -methyl-5-pyra-zolone,, 1- 2-e'thy'lph'enyl -3 -methyl-5-pyrazolon'e, l-[nap'hthyl-( 1)- or -(2) 1-3-methy1-5-pyrazolone, '1-phenyl-5-pyrazolone-3-carboxy1ic acid p'henylaniide, 1-n-octyl-3-methyl-5-pyrazolone, Hydroxyquinolines, Barbituric acid, Naphthalene derivatives, such as 6-bromo-, 6-rnethoxyor 6-methyl 2-aminonaphthalene, Z-phenylaminonaphthalene, Z-aminonaphthalene itself, and 2-aminonaphthalene-l-sulfonic acid which, as is known, couple to give the same dyestuffs as Z-aminonaphthalene, since the sulfonic acid group in the 1- position splits off, and also fi bromoor 6-methoxy-2- hydroxynaphthalene and especially l-acetylamino-7-hydroxynaphthalene, 1-n-butyrylamino-7-hydroxynaphthalene, 1-benzoylamino-7-hydroxynaphthalene, 1carbethoxyaminoJ-hydroxynaphthalene, ii-chloro-l-hydroxynaphthalene, S-chloro-l-hydroxynaphthalene, 5': 8-dichloro- 1 -hydroxynaphthalene, 5 8-dichloro-2-hydroxynaphthalene, .2-hydroxynaphthalene and if desired, l-hydroxynaphthalene, I 1-pheny1-3-methyl-5-pyrazolonee2'e, 3- or -4-sulfonic acid, 2-chloro-'1-pheny1-3emethyl-5-pyrazolone-4 or -5'su.l'

fonic acid, 2 5 -dichloro-1-phenyl-3 -methy1-5 -pyrazolone-4'-sulfonic acid,

-7'- or -8-sulfonic acid, l-[naphthyl-(Z')1-3-methyl-5-pyrazolonee2 or -8'-su1- ionic acid, :1-acetoacetylaminobenzeneA-sulfonic acid and especially .Z-aminoor 2-hydroXynaphtha1ene-4-, -'5-, -6- or -7-sul- 2-phenylamino-8-hydroxynaphthalene-6-sulfonic acid,

2-phenylamino-5-hydroxynaphthalene6 3 '-disulfonic acid.

'thalenes, meta-aminophenol, l-aryl-S-pyrazdlones which contain an amino group in the aryl radical, such as 1-(2- or -3- or -4-aminophenyl)-3-methyl-5-pyrazolone, 1-(3- or 4'-aminophenyl)-5-pyrazolone-3ecarboxylic acid, and

also fl-keto-carboxylic acid arylides containing an acylnaphthalene-3 :6-di sulfonic acid,

iitable aminoorhydroxylg'roup in the arylide radical, and amino-naphthol sulfonic' acids, suchas' Z-amino-8 hydroxynaphthalene- 6-sulfonic acid, 2-n-methylamino-8- hydroXynaphthalene-6-sulfonic acid, 2 alkylamino j-hydroxynaphthalene-7-sulfonic acid; l amino tl-hydroxy- V l-methylamino-8-hydroxy-naphthalene-3:6-disulfonic acid, ,Z-amino-S-hydroxynaphthalene-7-sulfonic acid, 2-(4'-aminobenzoylamino)--hydroxynaphthalene-7-sulfonic acid, 2-('4 aminophenylamino) 5 hydroxynaphthalene 3':7 disulfonic acid. It will be understood that when diazocomponents containing nitro groups or coupling components containing acylamino groups are used, the necessary acylatable groups, especially amino groups, are subsequently produced by reduction or hydrolysis. In selecting the diazo components and coupling components to be used care must be taken that only one of the dyestulfs to be used for making the complex chromium compounds of the invention should contain an acylatable group, in addition to the groups permitting the formation of complexes.

Inmaking the lzl-chromium complexes of ortho: ortho-dihydroxy-monoazo-dyestutfs they can. be made, as is known, not only from ortho:ortho-dihydroxy-monoazo-dyestuifs, but also from the corresponding ortho-alkoxy-ortho-hydroxy-monoazo-dyestufls. For making the chromiferous starting materials to be used in the process of the invention it is normally possible to use, instead of the ortho-hydroxy-diazo-compounds, the corresponding ortho alkoxy-diazo compounds, especially the methoxycompounds. As certain coupling components, for example 2-hydroxynaphthalene-8-sulfonic acid and 2-aminonaphthalene-8-sulfonic acid, are not capable of conpling with .ortho-hydroxy1diaio-compounds, there is the alternative of using lzl-coinplexes of dyestuffs which contain the radical of such a coupling component.

The lzl-complexes used as starting materials may, in other respects, be prepared by methods in themselves known, for example, by reacting the chromium-free monoazo-dyestuifs, advantageously those containing a tained, which contains two exchangeable halogen atoms, a further halogen atom is reacted with ammonia 'orz an organic mercapto or hydroxy-compound or an organic I amine possessing ornot possessing the character of a dyestufi in such manner that a metallif erous :monjo'azo' low a temperature as possible and in the presence of an sulfonic acid group, in an acid medium with an excess of a salt of trivalent chromium, such as chromium for mate, chromium sulfate or chromium fluoride, at the 'boil or, if desired, at a temperature above 1001" C.

The reaction of the lzl-chromium complexes with the chromium-free dyestuffs may be carried out in an organic solvent, if the dyestuff contains no groups imparting solubility in water, but is advantageously carried out in an aqueous neutral to weakly alkaline medium under atmospheric or superatmospheric pressure at the ordinary or a raised temperature, for example, at a temperature within the range of C. to 120 C. It is generally desirable to react with one another the chromiferous 1:1- complex and the chromium-free dyestufi in quantities that are as near ,as possible to equivalent quantities, the molecular ratio of metal-free dyestutf to lzl-complex being advantageously at least 0.85:1 and at most 120.85. The

acid-binding agent or if desired in an organicsolvent.

In another form of the process the condensation with cyanuric chloride or with one of the aforesaid 2:4-dihalogen-1:3:5-triazines, for example, a dihalogen-triazine compound of the Formula'2, may be carried out before reacting the chromium-free monoazo-dyestutf with the chromiferous monoazo-dyestufi provided that these dyestufis react with one another so readily to form the 1:2- complex that the halogen present in the triazine nucleus in one of the dyestuits is not attacked.

The dyestufis of this invention, which are new, are valuable dyestuifs and are suitable for dyeing or printing a very wide variety of materials such as wool, superpolyamides, silk, leather, and especially polyhydroxylated materials offibrous structure such ascellulosic materials and also synthetic fibers, for example, of regenerated cellulose, or natural materials'such as cellulose, linen or especially cotton. {They are suitable for dyeing cellulose fibers by the so-called direct dyeing methods from long liquors consisting of alkaline aqueous baths, which may have a high concentration of salt, and especially by printing andso'called pad dyeing processes, in which the dyestuit is applied to the material to be dyed by printing or padding and the dyestutf is fixed on the material by means of an acid-binding agent. r P

The dyestufis can be isolated, advantageously at a low temperature, by salting out and filtration. The filtered which the dyestuif is produced 'may be subjected to spray nearer this; ratio is to 1:1, themore advantageous, in

general, is the result.

The condensation of these asymmetrical complex chro mium compounds of monoazo-dyestuifs containing an aoylatable amino group with cyanuric chloride or a dihalogentriazine compound, for example, withthe 'compound of the Formula 2 is advantageously carried out in the presence of an acid-binding agent, such as sodium acetate, sodium hydroxide or sodium carbonate, under conditions such that the final product contains at least r s r rwit a asur l de. es l gye chloride, and in the primary condensation product so ohexample, by 10 or 1000 times, without difiiculty. If the dyestuffs used as starting materials are not in "a pure a form, for example, are not closely defined dyestufi acids; 1, or dyestutf salts, but contain foreign substances, for example, resulting from precipitationby salting'out, and

which substances have substantiallyno harmful effect on the reaction in question, the dyestutfs can generally be successfully used in that form. 7 However, it is then de-"e V sirable to determine their content of pure dyestutf by any 7 a n m fl d or exa pl y the titration 9 It will j be Example 1 0.02 mol of the complex chromium compound -containing one atom of chromium per molecule of thedyestuff from 6-nitro-1-diazo-2-hydroxynaphthalene-4-si1lfonic acid and 2-hydroxynaphthalene is heated to 90 C.

with 0.02 mol of the dyestuif obtained by coupling diazotized -nitro-2-amino-l-hydroxybenzene in an alkaline medium with 2-amino-5-hydroxynaphthalene-7-sulfonic acid, in 400 cc. of water with the gradual addition of cc. of a 2 N-solution of sodium carbonate, and the mixture is maintained at 90 C. for about one hour.

The resulting solution of the mixed chromium complex after being cooled with ice to 0 C., is mixed with a solution of 3.7 grams of cyanuric chloride in cc. of acetone. The condensation is carried out at 0-5" C. with the gradual addition of about 10 cc. of a2 N-solution of sodium hydroxide so as to maintain the pH value of the reaction mixture throughout at about 6.5-7.

The resulting solution of the dichloro-triazine derivative is saturated with sodium chloride, the precipitated metalliferous dycstufi is filtered off, and the filter cake, after being mixed with 5 grams of a mixture of equal parts of monosodium and disodium phosphate, is dried Example 2 A solution of the dichlorotriazine derivative obtained as described in the first two paragraphs of Example 1 is mixed with cc. of a 2 N-solution of ammonia, and the mixture is heated ina flask provided with'an ascendingtube for 4 hours at -40 C. There is obtained an amino-monochlorotriazine derivative which can 1 be isolated by salting out and filtration. After drying the dyestutf so obtained, it is a grey powder which when used for dyeing cotton in the manner described in Example 4 produces a grey dyeing whichisfast toh'ghf II in OH 1 -N=N .r'

HOrS

reddishuavy 2 N=N--C\ blUe.

C" N OzN 11038 i CH:

. on OH 7 3 N=N blue green.

Hots (MN 7 Bots-- NH:

. OH i 1 OH 6 v NH t 4 N=N-C red.

HO s C=N Q h a I V HI OH l|-IH5 5 N=N N= QNHr' brown.

-CH| OH NO: Ht

In an analogous manner the monoazo-dyestufis named anuric chloride to give dichlorotriazme derivatives, which in column I of the following table are converted into 1:1- are reacted with m smmpounds named in column In complex chrommm compounds; and the latter are reacted with the dyesmfis named in column H to form mixed to y1eld monochlorotnazme denvatlves WhlCh dye cellu- 5 lose fibers the tints given in column IV.

The latter are reacted withcychromium complexes.

m a or a; m m .1 g. f I V l .V. N mm m mm mm m am a on 0 I do .0 H 0 o o my a k V l B B .S I m H m n w V m m w 7 km v m m N, m n n n n n A n m a m E H. I w .7 v H o o N ,r o NAT n n o n m OIC x N N. m N m w m a c O O V a H. L L

* I J r H v a on a A O OH on v m 0' NH"; N=N C V =N 2H:- y

o=N Hots 6H H0: H0: NH:

. 03 .011 A O on on HO,CaH4-NH, reddish r grey.

HOxB

Eicampled i is added to an ice-cold neutralized aqueous solution of afield :parts of .lyaminobenzene-ysulfonic acid,- and" the :mixture is neutralizedby the gradual addition of a dilute V .wsolution o'f ss'odium.:;hydroxide1'to neutralise .the' acid liberated. When amino groups can no longer be detected, there is added to the solution of the resulting primary condensation product a neutral solution ofthe 1:2-chromiurn mixed complex obtained as described in the first paragraph of Example 1 and, after the addition of 2 parts of sodium bicarbonate, the whole is heated for 2-4hours at C. The monochlorotriazinedyestufl so formed is precipitated by the addition of sodium chloride, and filtered ofi and dried. It dyes cotton grey tints.

For making the primary condensation product there may be used, instead of 1- aminobenzene-3-sulfonic acid, other amines for example, l-aminobenzene-Z-sulfonic acid, l-aminobenzene-Z-carboxylic acid, l-aminobenz ene- 2:5-disulfoni'c acid or 2-aminonaphthalene-4:8-disulfonic acid, whereby dyestulfs having similar properties are obtained.

a Example 4 i 0.1 mol'of the complex chromium compound containing one atom of chromium per molecule of dyestuif and obtained item the dyestufi obtained from 6-nitro l-diazoi Z-Lhydrox ynaphthalene 4 sulfonic f acid rand 2;hydroxynaphthalene is dissolved in 2000 parts ofwater' with 0.1 1 first paragraph of this examplerthe reaction mixture "be OH OHS-CHI greenish omo-onrcm-cHrNmLlQ.

mol "of the dyestufi obtained by coupling diazotized 5- nitro-Z-amino-l-hydroxybenzenerin an alkaline medium with 2-phenylarninm8'ehydroxynaphthalene-6:3-disulfonic acid followed by reduction of the "nitro group" to the amino group by means of'sodium sulfide, and the solution is neutralized with sodium carbonate. The mixture is then h'ea'ted'in-the cOurse of /2 hour toj8Q90 6., car'ebeing taken by. theaddition of sodiumfcarbonate that-the dyestuif solution has a'weakly' alkaline reaction.

The :wholeis maintained for one hour at 80 C., during which thepI- I; value of the solution no longer changesg 5 p The cooled solution'of the resulting l:-2-chromi umi complex: is added to a fine aqueous ice-cold suspension of 18.5 parts :of .rcya'nuric chloride-in- 400 parts orwater, and the reaction'of the mixture'ismaintained -neutral the gradual addition of dilute caustic soda soluw j .tion. =-When the condensation is finished} there areadd'ed 50 parts of an ammonia solution of 10%"strength-and the whole is stirred for 2 hours at 40 C., during which one chlorine atom is replaced by a free amino group.' The dyestufi formed is salted out, and separated by til-V tration and dried.-

It dyes cotton by the method described in Example reddish grey tints. 7

By condensing at 4-0'C. 18 parts of 2:4 dichloro-6- methoxy-lz3z5-triazine, which has been dissolved ii vparts of acetone, with the neutral solutioniof thef1:2- mixed chromium complex obtained as described in the r arose-&4

.ing maintained neutral by the.gradual addition ofa dilute 7 solution of sodium hydroxide, there'is obtained a monochlorotriazine dyestufi whichllikewis'e dyes cotton reddish grey tints which are fast to washing.

A dyestuif having similar properties is obtained by using 24.3 parts of 2 2 4-dichloro- 6;phenoxy- 1 :3 Sdriazine, instead of 18 parts of 2:4-dichloro-6-methoxy-'d:325- triazine. ly carried out in aqueous acetone.

Example 5 1 part of the dyestufii obtained Fas described in Example 4 is dissolved in 100 parts of water. A cotton fabric is impregnated with the solution on a foulard and then squeezed to remove the excess liquid until it retains 75% of its weight of dyestuff solution. The "imp'regnated material .is :dried, then impregnated "at room 7 temperature in a solution containing, per liter, l0:grarns of sodium hydroxide and 300 grams of sodium chloride, the material .is squeezed to a weight increase of 75%, and then steamed for 60 seconds at 100-l01 C. The material is then rinsed and the dyeing is treated with water at the boil for hour, and then rinsed in the cold and dried. There is obtained a reddish grey dyeing which is fixed fast to light.

What is claimed is:

1. 'A complex chromium compound containing one atom of chromium bound .in complex union with two molecules of different monoazo dyestuifstofwhich one 7 corresponds to the formula HO-R- wherein R represents a naphthalene radical bound to the azo linkage in vicinal position to the hydroxyl group, and R represents =a Z-hydroxynaphthalene radical bound to the azo linkage in position 1 and the other is a member selected from the group consisting of dyestuffs corresponding to the formula 1 'wherein R represents a member selected from ithei-group consisting of a benzene and anaphthalene radical bound ,tothe azollinkage'in'vicinal .position'tothezhydroxyl group .and Xrepresents amember selected :from the group consisting of Cl, an NH; group, the aminobcnzene .i'adical C H NH-,, the radical of an aminohenzene. sulfonic acid bound by its amino lgrou'p, and the lradical'of an aminobenzoic acid bound by its amino 1 group.

2. .A complex chromium-compound containing .one atom of chromium bound in com-plex union with two molecules-of different monoazo dyestuiis of which-one corresponds to the formula 7 In this case the condensation is advantageousand '16 wherein A represents a member selected incur the group consisting of Z-hydroxy-naphthalene bound to the azo linkagejn lepo'sition, and .Lphenyl -methyl-5- py1:azolone bound in 4-position to the azo linkage and X is a member of the group consisting O'fhydrogen and the group NO, and the other corresponds toth'e'formula on E1 3- =N 10 N I 1 Hots NBC-43 (5-4:

16 wherein R represents amember selected from the group consisting of a-nitrated benzene radical bound to therazo' linkage in a position vicinal to a hydrox-yl/gr'oup andthe radical of a 6 nitro-2-hydroxy-naphthalene sulfonic acid bound to-the a'zo linkage in l-position and Xzrepresents 20 a 'member selected from the group consistingof an NH,

group, the radical of an amino-benzene sulfonic acid bound by its amino group, and the radical of an aminobenzoic acid bound by its amino group.

3. A complex chromium compound containing tone 25 atom of chromium bound in complex union with itwo molecules of two dilferent monoazo dyestuffs of which one corresponds to the formula 4. The complex .ehromium eompeund containing atom of; chromium bound sin complex union with one molecule of: eachmf the mouoazn'dyestufis of the formulde i The complex chromium compound conta idiiig Lone atom ofchromium bound in complex :Oue

molecule of each of the monoazo dyestufis' of the 8. The complex chromium compound containing one 7 I formulae atom of chromium bound in complex union with one 011 molecule of each of the monoazo dyestuffs of the formulae on on E1 16 r f N 7 H 0H 7 01 out Hols NH-b s-o1 a N=N \N 6. The complex chromium compound containing one A NH 2 atom of chromium bound 1n complex umon with one molecule of each of the monoazo dyestuffs of the formulae N V 80 9. The complex chromium compound containing one atom of chromium bound in complex combination with one molecule of each of the monoazo dyestuffs of the formulae N0:

85 and C1 7 OH OH 7. The complex chromium compound containing one atom of chromium bound in complex unlon with one and molecule of each of the monoazo dyestuffs of the formulae 3 on $033 3 N=N NHO N/ N HaN- -nN H088 OH OH References Cited in the file of this patent UNITED STATES PATENTS 1,779,298 Straud et a1. Oct. 21, 1930 d 2,012,779 Straud et a1 Aug. 27, 1935 

1. A COMPLEX CHROMIUM COMPOUND CONTAINING ONE ATOM OF CHROMIUM BOUND IN COMPLEX UNION WITH TWO MOLECULES OF DIFFERENT MONOAZO DYESTUFFS OF WHICH ONE CORRESPONDS TO THE FORMULA HO-R-N=N-R1 WHEREIN R REPRESENTS A NAPHTHALENE RADICAL BOUND TO THE AZO LINKAGE IN VICINAL POSITION TO THE HYDROXYL GROUP, AND R1 REPRESENTS A 2-HYDROXYNAPHTHALENE RADICAL BOUND TO THE AZO LINKAGE IN POSITION 1 AND THE OTHER IS A MEMBER SELECTED FROM THE GROUP CONSISTING OF DYESTUFFS CORRESPONDING TO THE FORMULA 